CN105695953B - A kind of preparation method and application of three-dimensional carbon negative pole material - Google Patents

A kind of preparation method and application of three-dimensional carbon negative pole material Download PDF

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CN105695953B
CN105695953B CN201610035653.2A CN201610035653A CN105695953B CN 105695953 B CN105695953 B CN 105695953B CN 201610035653 A CN201610035653 A CN 201610035653A CN 105695953 B CN105695953 B CN 105695953B
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carbon material
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CN105695953A (en
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郭玉国
叶欢
殷雅侠
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Institute of Chemistry CAS
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H01M4/0428—Chemical vapour deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a kind of preparation method and applications of three-dimensional carbon material.The three-dimensional carbon material is modified by Nano carbon balls, and Nano carbon balls are to be curled into class onion like structure by graphite flake.Carbon material of the present invention realizes the preparation of class onion structure carbon ball using chemical vapour deposition technique.The three-dimensional carbon material can realize reversible embedding removing sodium, and ramp type voltage behavior is presented, and solve secondary battery cathode material dendritic growth prepared by existing method, battery security is improved, improvement specific capacity is low, and stability is poor, poor circulation, the problems such as discharge platform height and for the first time coulombic efficiency be low.The negative material is directly used as electrode using nickel foam as skeleton, and binder free is at low cost, and method is simple, is suitble to large-scale production, has application potential.

Description

A kind of preparation method and application of three-dimensional carbon negative pole material
Technical field
The invention belongs to field of electrochemical power source, and in particular to a kind of secondary cell three-dimensional carbon negative pole material and its preparation Method and the secondary cell using the carbon material.
Background technology
The becoming increasingly conspicuous of the continuous consumption of fossil energy and environmental problem promotes people to research and develop high-energy density, high power capacity Electrochemical energy storage system.Lithium ion battery because its energy density is high, have extended cycle life due to be widely studied.Be then subjected to lithium from The limitation of sub- battery energy density and natural resources, lithium ion battery cannot already meet large-scale energy storage system application.From energy From the point of view of source development and the long-range demand utilized, developing is become currently based on resourceful and reasonable price secondary cell system Goal in research.Compared to lithium, reserves of the sodium resource in the earth's crust account for about 2.74%, and sodium element is widely present in ocean, It is evenly distributed on the earth, physical property is similar to lithium so that the secondary sode cell based on reversible charge and discharge becomes the strong of lithium electricity It substitutes.However sodium ion radius is significantly larger than lithium ion radius, it is larger so as to be generated during sodium ion intercalation/deintercalation Distortion of lattice.Therefore the development bottleneck of sodium-ion battery is to lack suitable storage sodium electrode material (including anode and cathode). Most of sodium-ion battery positive material is by anode material for lithium-ion batteries differentiation and come such as：NaCoO2And LiCoO2.Nearest picture Na3V2(PO4)3,NaNi1/3Fe1/3Mn1/3O2Also there is relevant report with prussian blue novel anode material.Possibly serve for sodium at present Ion battery cathode mainly has alloy type negative material, inlaid scheme negative material and carbon based negative electrodes material etc..Alloy anode With specific capacity height, the advantages such as embedding sodium current potential is low, but alloy anode can cause big volume swollen when sodium ion is embedded in Swollen and contraction, causes capacity attenuation fast, coulombic efficiency is low.Inlaid scheme negative material such as Na0.66Li0.22Ti0.78O2It is recycling Volume change is small in the process, but the embedding sodium current potential of this kind of material is high, and specific capacity is low, and electron conduction is poor.Carbon material is because of its conduction Property it is good, have good layer structure, be suitable for the insertion and abjection of metal ion.Then, graphite material, a kind of lithium-ion electric Common negative material in pond, since interlamellar spacing smaller (0.34nm) is not suitable for use in sodium-ion battery cathode.Hard carbon material, Degree of graphitization is relatively low, and interlamellar spacing is larger and structural disorder, is suitble to the insertion and abjection of sodium ion.But the hard carbon reported at present Material, specific capacity are mainly by the platform contribution close to very long deintercalation sodium ion of 0V or so, this precipitation with metal Current potential relatively, can cause overcharge or low temperature charging process to form dendrite in carbon electrodes precipitating metal and cause short circuit, Cause safety problem.In addition, the preparation method of carbon negative pole material is comparatively laborious at present, low output, it is difficult to realize industrialization, apply Degree is low.The introducing of binding agent and conductive additive when preparing negative electrode simultaneously, reduces the content of Carbon anode active material, leads It causes to reduce with the matched full battery specific capacity of positive electrode, the energy density of battery system reduces.
Invention content
Technical problem solved by the invention is to overcome that existing carbon material safety is poor, and cyclical stability is poor, cost The defects of height, preparation process is not suitable for industrialized production.It provides and a kind of prepares simple, at low cost, binder free, cyclical stability Good, capacity is high, can large-scale production and comparatively safe secondary cell three-dimensional carbon negative pole material and preparation method thereof.
The present invention solves its technical problem the technical solution adopted is that a kind of three-dimensional carbon negative pole material of binder free, be by It is completed according to following steps：
(1) (commodity) three-dimensional template is cleaned, dried, and annealing removes three-dimensional template under certain temperature, reducing atmosphere The oxide layer on surface.
(2) three-dimensional template that step (1) obtains is placed in CVD tube furnaces, is passed through carbon containing carrier gas, in certain deposition velocity Under, it is made to crack deposition carbon in three-dimensional template, the carbonaceous amount of deposition is 1-30mg/cm2, preferably 10-30mg/cm2, more preferably 10-20mg/cm2.Annealing conditions wherein described in step (1) are：Temperature is 800-1000 DEG C, preferably 850 DEG C -950 DEG C, more excellent Select 900 DEG C, heating rate is 2-20 DEG C/min, preferably 5-10 DEG C/min, more preferable 10 DEG C/min, sintering time 10- 120min, preferably 10-30min, more preferable 30min.
Three-dimensional template described in step (1) is selected from following at least one：Nickel foam, foam copper, foamed aluminium, titanium foam.
Reducing atmosphere described in step (1) is H2Or the mixing of the inert gases such as the reducing gas such as CO and argon gas or nitrogen Volume ratio shared by gas, wherein reducibility gas is 2-50%, preferably 5-20%.
Carbon containing carrier gas described in step (2) is selected from following at least one：Methane, ethane, propane, butane, ethylene, propylene, Acetylene, benzene, toluene.
Deposition velocity described in step (2) is controlled by controlling the flow of carrier gas, and the flow of preferably carbon containing carrier gas is 255-550sccm, preferably 280-380sccm.
The condition of chemical vapor deposition described in step (2) is：Depositing temperature is 600-1300 DEG C, preferably 850-950 DEG C, more preferable 900 DEG C, heating rate is 2-20 DEG C/min, and preferably 5-10 DEG C/min, more preferable 10 DEG C/min, sedimentation time is 2-30min, preferably 5-10min, more preferable 10min, the thickness of deposition is 1-30mg/cm2, preferably 10-20mg/cm2, more Preferably 10mg/cm2。
The Nano carbon balls are curled into class onion-like structure by graphite flake.Nano carbon balls diameter 600-3000nm it Between, preferably 1000-2000nm.
It is a further object to provide the applications of the three-dimensional carbon material.
Application provided by the present invention is application of the three-dimensional carbon material as battery electrode material, preferably sodium ion and lithium from The application of sub- cell negative electrode material, the application of more preferable anode material of lithium-ion battery.
Compared with prior art, preparation method provided by the invention is at low cost, can prepare with scale, good cycling stability, And ramp type voltage behavior is presented to metallic sodium in obtained three-dimensional carbon negative pole material, avoids that dendrite is precipitated, improves cell safety Property, conventional electrode materials is overcome to introduce binding agent and the shortcomings that conductive additive in addition, improve negative electrode active material in electrode In content.
Description of the drawings
Fig. 1 is the electron scanning micrograph of the three-dimensional porous foams nickel surface of embodiment 1.
Fig. 2 is that the three-dimensional porous foams nickel surface of embodiment 1 deposits the low power electron scanning micrograph of carbon ball.
Fig. 3 is that the three-dimensional porous foams nickel surface of embodiment 1 deposits the high power electron scanning micrograph of carbon ball.
Fig. 4 is that the three-dimensional porous foams nickel surface of embodiment 1 deposits the high power cross sectional scanning electron microscope photo of carbon ball.
Fig. 5 is that the three-dimensional porous foams nickel surface of embodiment 1 deposits constant current charge-discharge curve of the carbon ball to sodium.
Fig. 6 is the electron scanning micrograph of comparative example 3.Fig. 7 is the three-dimensional porous foams nickel surface deposition of comparative example 4 The low power electron scanning micrograph of carbon pipe.
Fig. 8 is the high power electron scanning micrograph of the three-dimensional porous foams nickel surface deposition carbon pipe of comparative example 4.
Fig. 9 is constant current charge-discharge curve of the three-dimensional porous foams nickel surface deposition carbon pipe to sodium of comparative example 4.
Specific embodiment
With reference to specific embodiment, the invention will be further described, but the present invention is not limited to following embodiments.
Experimental method described in following embodiments is conventional method unless otherwise specified；The reagent and material, such as Without specified otherwise, commercially obtain.
Embodiment 1
(1) three-dimensional carbon negative pole material is prepared
(1) commercial foam nickel is cleaned, dried, and at 900 DEG C, H2(H under/Ar mixing reducing atmospheres2/ Ar mixed gas Volume ratio be 5:95) annealing 30min removes the oxide layer of foam nickel surface.It can be with from the electron scanning micrograph of Fig. 1 See that foam nickel surface is smoother, and be three-dimensional porous structure, aperture is 50-150 μm.
(2) nickel foam after annealing is placed in CVD tube furnaces, be passed through containing C2H2Carrier gas, with the speed liter of 10 DEG C/min Temperature treats that temperature rises to 900 DEG C and starts to deposit, and controls C2H2Flow for 360sccm, under this deposition velocity, 900 DEG C of depositions 10min, the carbonaceous amount of deposition is 10-20mg/cm2。
The Carbon deposition is clear that on the skeleton of porous foam nickel from the electron scanning micrograph of Fig. 2, Skeleton becomes more coarse by original smoother surface, and Fig. 3 is the electron scanning micrograph of Fig. 2 amplification factors, from In it can be seen that the carbon pattern of deposition for ball shape structure, a diameter of 1-2 μm of carbon ball, Fig. 4 is single carbon ball cross-section diagram in Fig. 3, Therefrom it can be seen that the carbon ball of deposition is the class onion curled by graphite flake layer like structure.Between graphite flake layer between suitable hole Away from the storage for being conducive to sodium ion.
(2) battery assembles
Working electrode is the carbon of deposition, is metallic sodium to electrode, is inserted into glass fibre membrane (Whatman companies of Britain) conduct Diaphragm adds in 1M NaClO4EC/PC (mass ratioes 1:1) solution.
(3) battery testing
The battery of above-mentioned assembling is subjected to charge-discharge test on charge-discharge test instrument, the charge and discharge section of test is 0.01–3.0V.Test temperature is 25 DEG C.Fig. 5 is constant current charge-discharge curve of the battery under 20mA/g current densities, Under 20mA/g current densities, first charge discharge efficiency reaches 80%, and reversible discharge specific capacity reaches 170mA h/g.
Embodiment 2
Difference from Example 1 is only that three-dimensional carbon material, and the carbon ball gas is methane, CH4Flow be 320sccm, 1000 DEG C of deposition 8min, through characterization, the carbon distribution uniform of the Carbon deposition of deposition, quality 10-15mg/cm2, carbon A diameter of 1100-1400nm of ball.Using the three-dimensional carbon material of deposition as working electrode, metallic sodium is to electrode, is inserted into glass Tunica fibrosa (Whatman companies of Britain) adds in 1M NaClO as diaphragm4(EC/PC) carbonic ester electrolyte.0.01-3.0V, Under 20mA/g current densities, first charge discharge efficiency 78%, reversible discharge specific capacity reaches 140mA h/g
Embodiment 3
Difference from Example 1 is that (one) prepares three-dimensional carbon material, the C2H4Flow for 290sccm, 800 DEG C Deposit 4min.Through characterization, the carbon distribution uniform of deposition, quality 1-5mg/cm2, a diameter of 1000-1200nm of carbon ball.With For the carbon three-dimensional carbon material of deposition as working electrode, metallic sodium is to electrode, is inserted into glass fibre membrane (Whatman companies of Britain) As diaphragm, 1M NaPF are added in6(EC/DEC) (mass ratio 1:1) solution.It is first under 0.01-3.0V, 20mA/g current density Secondary efficiency is 75%, and reversible discharge specific capacity reaches 150mA h/g.
Embodiment 4
Difference from Example 1 is only that three-dimensional carbon material, C in step 2 in embodiment 13H6Flow be 255sccm, 1000 DEG C of deposition 15min.Through characterization, the carbon distribution uniform of deposition, quality 20-30mg/cm2, carbon ball it is straight Diameter is 2-10 μm, and using three-dimensional carbon material as working electrode, metallic sodium is to electrode, is inserted into glass fibre membrane (Britain Whatman Company) as diaphragm, add in 1M NaTFSI (DOL/DME) (mass ratio 1:1) solution.0.01-3.0V, 20mA/g electric current are close Under degree, first charge discharge efficiency 70%, reversible discharge specific capacity reaches 130mA h/g.
Comparative example 1
Difference from Example 1 is only that three-dimensional carbon material, the C2H2Flow for 220sccm, 900 DEG C of depositions 6min.Through characterization, the carbon of deposition is made of minute quantity carbon nanotube and most of carbon ball, and caliber is about in 1000nm, the ruler of carbon ball Very little is 800-1000nm, deposition quality 1-6mg/cm2.Using the three-dimensional porous material that carbon ball is modified as working electrode, metal Sodium is to electrode, is inserted into glass fibre membrane (Whatman companies of Britain) as diaphragm, adds in 1M NaClO4(EC/DEC) (quality Than being 1:1) solution.Under 0.01-3.0V, 20mA/g current density, first charge discharge efficiency 68%, reversible discharge specific capacity reaches 125mA h/g
Comparative example 2
Difference from Example 1 is only that three-dimensional carbon material, the C2H2Flow for 140sccm, 800 DEG C of depositions 12min.Through characterization, through characterization, the ratio of carbon nanotube and carbon ball respectively accounts for half, and distribution uniform, caliber is about in 600nm, carbon The size of ball is 900nm, deposition quality 1-12mg/cm2.Using the three-dimensional porous material that carbon ball is modified as working electrode, gold It is to electrode to belong to sodium, is inserted into glass fibre membrane (Whatman companies of Britain) as diaphragm, adds in 1M NaPF6(EC/DEC/DMC) (mass ratio 1:1:1) solution.Under 0.01-3.0V, 20mA/g current density, first charge discharge efficiency 64%, reversible discharge specific capacity Reach 115mA h/g
Comparative example 3
Difference from Example 1 is in three-dimensional carbon material, the C2H2Flow for 80sccm, 850 DEG C of deposition 10min.From The electron scanning micrograph of Fig. 6 it is clear that the carbon of deposition is made of most of carbon nanotube and a small amount of carbon ball, point Cloth is more uniform, orientation disorder, mutually winds, and for caliber about in 180nm, the size of carbon ball is 200nm, deposition quality 1-8mg/ cm2.Using the three-dimensional porous material that carbon ball is modified as working electrode, metallic sodium is to electrode, is inserted into glass fibre membrane (Britain Whatman companies) as diaphragm, add in 1M NaClO4(EC/DEC/DMC) (mass ratio 1:1:1) solution.0.01-3.0V, Under 20mA/g current densities, first charge discharge efficiency 64%, reversible discharge specific capacity reaches 90mA h/g.
Comparative example 4
Other conditions are same as Example 1, and the difference lies in C in step 2 in embodiment 12H2Flow for 50sccm, 650 DEG C of deposition 10min.It can see what the deposition on three-dimensional foam nickel obtained from the electron scanning micrograph of Fig. 7 and Fig. 8 Carbon pattern is carbon nanotube.A diameter of 50-200nm of carbon nanotube, the length of carbon nanotube is 1-10 μm.With three-dimensional carbon material For working electrode, metallic sodium is to electrode, and glass fibre membrane (Whatman companies of Britain) adds in 1M NaClO as diaphragm4 (EC/DEC) carbonic ester electrolyte.Fig. 9 be the battery under 0.01-3.0V, 20mA/g current densities, first charge discharge efficiency is 60%, reversible discharge specific capacity reaches 80mA h/g.
Comparative example 5
Other conditions are same as Example 1, and carbon containing carrier gas described in step 2 is CH to difference in embodiment 14, CH4 Flow with carrier gas is 120sccm, 1000 DEG C of deposition 10min.After tested, modified three-dimensional porous material surface is by graphene structure Into the thickness of graphene is 5-10 atomic layer.It is gold to electrode using the three-dimensional porous material of graphene modified as working electrode Belong to sodium, glass fibre membrane (Whatman companies of Britain) adds in 1M NaClO as diaphragm4(EC/PC) carbonic ester electrolyte. Under 0.01-3.0V, 20mA/g current density, first charge discharge efficiency 55%, reversible discharge specific capacity reaches 95mA h/g.

Claims (7)

1. a kind of preparation method of three-dimensional carbon material, it is characterised in that：The method is as follows：
（1）Commodity three-dimensional template is cleaned, is dried, and annealing removes three-dimensional template surface under certain temperature, reducing atmosphere Oxide layer；
（2）By step（1）Obtained three-dimensional template is placed in CVD tube furnaces, is passed through carbon containing carrier gas, under certain deposition velocity, It is made to crack deposition carbon in three-dimensional template, the carbonaceous amount of deposition is 1-30 mg/cm2, obtain the three-dimensional carbon of Nano carbon balls modification Material；
Step（1）The annealing conditions are：Temperature is 800-1000 DEG C, and heating rate is 2-20 DEG C/min, and sintering time is 10-120 min；
Step（2）Described in carbon containing carrier gas be acetylene；
Step（2）The deposition velocity is 280-380sccm, and the depositing temperature of the deposition is 820-950 DEG C, heating speed It spends for 2-20 DEG C/min, sedimentation time 5-15min, the thickness of deposition is 8-20mg/cm-2。
2. a kind of preparation method of three-dimensional carbon material according to claim 1, it is characterised in that：Step（1）Described in three It ties up template and is selected from following at least one：Nickel foam, foam copper, foamed aluminium, titanium foam；Step（1）Described in reducing atmosphere for choosing From H2Or the reducing gas of CO and the mixed gas of inert gas, wherein volume ratio shared by reducibility gas is 2-50%.
3. a kind of preparation method of three-dimensional carbon material according to claim 1, it is characterised in that：The Nano carbon balls of preparation are straight Diameter is 1000-2000nm.
4. a kind of preparation method of three-dimensional carbon material according to claim 1, wherein the Nano carbon balls are rolled up by graphite flake Song is into class onion structure.
5. the three-dimensional carbon material that any the method is prepared in claim 1-4.
6. application of the three-dimensional carbon material as secondary battery cathode material described in claim 5, the secondary cell for lithium from Sub- battery or sodium-ion battery.
7. application of the three-dimensional carbon material according to claim 6 as secondary battery cathode material, the secondary cell are Sodium-ion battery.
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US16/064,852 US10847804B2 (en) 2016-01-19 2016-04-25 Carbon nanosphere modified current collector for lithium metal battery and method for preparing the same
PCT/CN2016/080143 WO2017124659A1 (en) 2016-01-19 2016-04-25 A modified 3d current collector, its application in lithium metal batteries and method for preparing said composite material

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